Organic vapor phase deposition for the growth of large area organic electronic devices

Richard R. Lunt, Brian E. Lassiter, Jay B. Benziger, and Stephen R. Forrest Citation: Appl. Phys. Lett. 95, 233305 (2009); doi: 10.1063/1.3271797 View online: http://dx.doi.org/10.1063/1.3271797 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v95/i23 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 95, 233305 2009

Organic vapor phase deposition for the growth of large area organic electronic devices
Richard R. Lunt,1,2 Brian E. Lassiter,1 Jay B. Benziger,2 and Stephen R. Forrest1,a
1

Department of Electrical Engineering and Computer Science, Department of Physics, and Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109 USA 2 Department of Chemical Engineering, Princeton Institute for the Science and Technology of Materials (PRISM), Princeton University, Princeton, New Jersey 08544 USA

Received 7 August 2009; accepted 13 November 2009; published online 11 December 2009 We demonstrate that material utilization efciencies of 50% and deposition nonuniformities 2.5% are achievable over substrate diameters of 200 mm using a simplied, organic vapor phase deposition OVPD system. The OVPD system is used to demonstrate doped electrophosphorescent organic light emitting diodes whose performance is comparable to those grown by vacuum thermal evaporation. Through continuum modeling, we demonstrate that analogous systems whose chamber dimensions are comparable to the substrate width are scalable to substrate sizes of at least 1500 1800 mm2 with deposition nonuniformities between 1.5% and 2.5%. These results indicate that OVPD is useful in the large area deposition of displays, lighting, and other organic electronic devices. 2009 American Institute of Physics. doi:10.1063/1.3271797 Organic vapor phase deposition OVPD has been demonstrated to be an effective deposition technology for highperformance thin-lm organic photovoltaics,1,2 transistors,3,4 and light emitting diodes OLEDs.58 In OVPD, organic materials are thermally evaporated into an inert carrier gas stream that transports the molecules through a heated chamber. There, diffusive mixing generates a uniform organic ux that is physisorbed onto a cooled substrate.9,10 The hotwalled reactor avoids unwanted deposition on its surfaces, leading to efcient materials usage and reduced system down-time for cleaning. Preliminary studies on scaling to 400 400 mm2 Gen-2 substrates through the use of a complex and potentially costly closed-coupled showerhead for materials distribution over large substrate areas have recently been reported.11 Here, we investigate the scalability of a simplied OVPD chamber design to sizes that can accommodate 200 mm diameter substrates based on both experiment and simulation. We explore the possibility of scaling to even larger, Gen-6 1500 1800 mm2 size substrates. We show that a simple ow distribution system can produce both lm thickness uniformity and morphological control over large areas while avoiding the use of complex material distributors connected by lengthy organic source feed lines that can hinder scaling of the technology to very large substrates. 7,12 Using a prototype, automated, mid-size OVPD chamber that accommodates 200 mm diameter wafers, we show that material usage efciencies of 50% with variations in lm thickness 2.5% are achievable. With this system, we demonstrate the growth of green electrophosphorescent OLEDs PHOLEDs that exhibit performance comparable to those grown by vacuum thermal evaporation VTE. Based on these experiments, continuum uid dynamics modeling is used to investigate the scaling of OVPD to at least Gen-6 size substrates. Our results suggest that OVPD is scalable to very large substrates, making it a key growth technology for low-cost organic electronics.
a

The computer-automated vertical OVPD system13 consists of ten source plenums mounted radially along one end of a 250 mm diameter deposition chamber see Fig. 1. Each source is individually loaded into a 5 cm3 alumina source crucible. The crucible is linearly translated within a temperature gradient to generate a range of organic partial pressures. A plug-valve is used to shutter the organic ux entering the reactor vessel from the deposition plenum.2 Flux from each source is directed toward a cooled 260370 K substrate holder. The deposition chamber also acts as a diffusivemixing zone for organic dopants and hosts, eliminating the need for a material distributor.12 The system is equipped with

Electronic mail: stevefor@umich.edu.

FIG. 1. Color a Cross-section schematic of the experimental mid-scale OVPD system. The reactor chamber diameter is 250 mm. b Cross-section of the deposition source plenum. The source crucible is linearly translated along a temperature gradient heater to control organic source partial pressure. 2009 American Institute of Physics

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FIG. 2. Color a Measured data points and calculated lines material utilization efciency M for Alq3 growth in the automated OVPD system as a function of total ow rate Q at pressure P = 1 Torr, and as a function of P at Q = 200 SCCM. Also shown is the deposition thickness proles of 100 nm thick lms of Alq3 grown on a 200 mm Si wafer at P = 300 mTorr and Q = 100 SCCM top, right axes. The experimental uniformity of the Alq3 lm is 2.3% with rotation, and 5.0% without rotation. b Forward viewing external quantum symbols and luminous power efciency lines of OVPD and VTE grown, green emitting Irppy3 PHOLEDs. Devices with 0.785 mm2 active area grown by OVPD circle, solid line and by VTE triangle, short dash; device with 100 mm2 active area inset grown by OVPD square, dash-dot.

a shutter positioned over the substrate, a quartz crystal lmthickness monitor, a pressure-regulating buttery valve, and a trolley system for in vacuo substrate transfer to a VTE chamber for deposition of metal cathodes. Film thickness measurements14 were performed using a variable-angle spectroscopic ellipsometer. The uniformity of the deposition is calculated as the standard deviation of the thickness divided by the average thickness. Using the prototype, multisource OVPD system, the material utilization efciency M and deposition uniformity were measured for the archetype molecular solid tris-8hydroxyquinoline aluminum Alq3 grown on 200 mm diameter Si wafers for a range of conditions, as shown in Fig. 2a. It was found that M varies only weakly with background pressure P, but is more strongly dependant on the total deposition ow rate Q, as expected. As ow rate increases, both M and uniformity decrease due to an increase in convective transport that bypasses the substrate. Although the chamber pressure has only a small effect on M under equilibrium source conditions, it was found that higher pressures improved the deposition uniformity as the source velocities are decreased, consistent with the uniformity dependence on the total source ow rate. Also shown in Fig. 2a are the uniformities across 200 mm wafers, with and without rotation for a source owrate and pressure of Q = 50 SCCM SCCM denotes standard cubic centimeter per minute and P = 250 mtorr, respectively.

Without rotation the deposition nonuniformity is 5.0%, which is nearly identical to the simulated nonuniformity of 5.1%. Alternatively, the uniformity improves to 2.3% with rotation. These nonuniformities stem primarily from owinduced boundary-layer thinning near the sharp edge of the substrate that increases the diffusive ux and hence material build up. The uniformity can be improved by extending the substrate holder several centimeters beyond the substrate edge, increasing the diameter of the substrate chamber to signicantly larger than the substrate itself or redirecting the outlet ow orthogonal to the substrate see below. To determine the quality of the lms, high efciency green electrophoshporescent OLEDs or PHOLEDs were deposited on an indium tin oxide coated glass substrate in the following sequence:15 40 nm thick N , N-diphenyl-N , N-bis1-naphthyl-1 , 1 biphenyl-4 , 4 diamine -NPD hole transporting layer, 20 nm thick 4-bis9-carbazolyl-2 , 2-biphenyl CBP host layer doped with 6% by volume of tris-2-phenylpyridine iridium Irppy3, 10 nm thick bathocuproine BCP exciton and hole blocking layer, 20 nm thick Alq3 electron transport layer, and a LiF0.8 nm/Al 100 nm cathode deposited through a shadow mask. All the organics layers were grown via OVPD except the control device at a rate of 0.10.25 nm/s with rotation. The chamber temperature was 573 K, and the source temperatures for NPD 0.2 nm/s, CBP 0.25 nm/ s, Irppy3 0.02 nm/s, BCP 0.2 nm/s, and Alq3 0.2 nm/s were 538, 535, 523, 455, and 543 K, respectively, with a source ow of 50 SCCM, total ow rate of 150 SCCM, background pressure of 500 mTorr, and a substrate temperature of 300 K. Control devices with a similar structure were grown via VTE in a chamber with a base pressure of 106 Torr. The PHOLEDs were tested in air using standard procedures.16 A comparison between the performance of VTE and OVPD-grown PHOLEDs is shown in Fig. 2b. The 1 mm diameter OVPD and VTE devices are found to have similar peak forward viewing external quantum and power efciencies of 9.0% 0.3% and 21.0 1.2 lm / W, and 8.8% 0.4% and 24.2 1.5 lm / W, respectively. Similar devices grown by OVPD with a larger active area of 100 mm2 show nearly identical efciencies of 9.3% 0.5% and 23.8 1.5 lm / W. To understand the effects of scaling this system to even larger substrates, a continuum dynamics model was used to simulate the experimentally measured characteristics of the 250 mm diameter system. These simulations were then extended to a Gen-6 OVPD system with Cartesian symmetry.17 The continuum model of coupled energy, mass, and momentum NavierStokes balances was solved for the velocity, temperature, concentration ux, and pressure elds. The uid density gradient was assumed to be weakly varying, allowing us to model the uid as pseudocompressible: density gradients are ignored in the continuity equation but the density is allowed to vary as an ideal gas. The ow eld is, therefore, assumed to be only a function of the carrier gas i.e., dilute organic concentration. The temperature dependant viscosity and thermal conductivity of the nitrogen carrier gas used are = 1.73 105 T / 300 K kg / m s and k = 0.025 T / 300 K W / m K, respectively,18 where T is the local temperature in Kelvin. The diffusivity is calculated according19 to D = DoT3/2 / P, where D0 = 5.2 105 m2 Pa / s K3/2 is obtained for Alq3 using the kinetic

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FIG. 3. Color a Schematic of the continuum model simulations of a Gen-6 OVPD deposition tool along with the simulation mesh. b Simulated velocity and diffusive ux elds for pressure, P = 250 mTorr, carrier gas ow rate, Q = 1000 SCCM, and chamber length to width ratio, L / W = 1.0. c Simulated deposition uniformity as a function of ow rate Q in SCCM and chamber dimensions L / W for W = 1.8 m lines are guides to the eye. d Series of deposition proles as a function of ow rate Q in sccm at P = 250 mTorr, L = 1.8 m and W = 1.8 m. With increasing ow rate, the deposition prole approaches Gaussian as the ow-stream becomes jetlike.

natural convection eddies that can disrupt the ow pattern. Although not exhaustive, these simulations indicate that there are several chamber congurations, along with a range of operating conditions, that can lead to uniform deposition proles. In conclusion, we have demonstrated a simple OVPD deposition system that exhibits material usage efciencies up to 41% 5% and lm uniformities of 2%3% across 200 mm wafers without the need for showerheads or bafes. These results are in agreement with continuum dynamics simulations. This indicates that the scale-up of this system can lead to large-area deposition thickness nonuniformities of only 1.5%2.5% over Gen-6 substrates sizes. Additionally, we have shown that PHOLEDs grown by VTE and OVPD exhibit similar performance. This work demonstrates the potential of OVPD as a method for the deposition of large-scale PHOLEDs for white lighting and displays, as well as for a range of organic electronic applications. The authors thank Dr. Fan Yang for assisting in the early stages of machine design, and David Pitts and Andrew Bass from Angstrom Engineering Kitchener, Ontario for their expert advice and construction of the OVPD system. We also thank the Department of Energy EERE Program, Universal Display Corp., and Global Photonic Energy Corp. for their support of this work.
F. Yang, M. Shtein, and S. R. Forrest, Nature Mater. 4, 37 2005. F. Yang, K. Sun, and S. R. Forrest, Adv. Mater. 19, 4166 2007. 3 C. Rolin, S. Steudel, K. Myny, D. Cheyns, S. Verlaak, J. Genoe, and P. Heremans, Appl. Phys. Lett. 89, 203502 2006. 4 M. Shtein, J. Mapel, J. B. Benziger, and S. R. Forrest, Appl. Phys. Lett. 81, 268 2002. 5 M. A. Baldo, V. G. Kozlov, P. E. Burrows, S. R. Forrest, V. S. Ban, B. Koene, and M. E. Thompson, Appl. Phys. Lett. 71, 3033 1997. 6 Y. R. Sun, M. Shtein, and S. R. Forrest, Appl. Phys. Lett. 86, 113504 2005. 7 T. X. Zhou, T. Ngo, J. J. Brown, M. Shtein, and S. R. Forrest, Appl. Phys. Lett. 86, 021107 2005. 8 M. Bsing, F. Zimmerman, F. Lindla, P. van Gemmen, D. Bertram, N. Meyer, D. Keiper, M. Heuken, H. Kalisch, and R. Jansen, Mater. Res. Soc. Symp. Proc. 1154, 1154 2009. 9 M. Baldo, M. Deutsch, P. Burrows, H. Gossenberger, M. Gerstenberg, V. Ban, and S. Forrest, Adv. Mater. 10, 1505 1998. 10 M. Shtein, H. F. Gossenberger, J. B. Benziger, and S. R. Forrest, J. Appl. Phys. 89, 1470 2001. 11 B. Marheineke, Proc. SPIE 5961, 596101 2005. 12 M. Schwambera, M. Gersdorff, N. Meyer, M. Reinhold, G. Strauch, M. Heuken, B. Marheineke, T. McEntee, S. Hartmann, W. Kowalsky, C. Himcinshi, and D. Zahn, Proceedings of the 8th Asian Symposium on Information Display ASID04, 2004, p. 370. 13 System assembled by Angstrom Engineering. 14 Material utilization efciency was calculated as the mass deposited on a 200 mm Si wafer divided by the mass of source material loaded. The deposited mass was estimated by the lm thickness and the lm density i.e., density of Alq3 = 1.55 gm / cm3. 15 M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, and S. R. Forrest, Appl. Phys. Lett. 75, 4 1999. 16 S. R. Forrest, D. D. C. Bradley, and M. E. Thompson, Adv. Mater. 15, 1043 2003. 17 Comsol Multiphysics v3.2. 18 M. Shtein, Ph.D. thesis, Princeton University, 2004. 19 R. Bird, W. Stewart, and E. Lightfoot, Transport Phenomena Wiley, New York, 2002.
1 2

theory of gases, and P is the chamber pressure. The inlet organic concentration was xed,10 and the concentration at the cooled substrate nonrotating was assumed to be 0 corresponding to a molecular sticking coefcient of 1. A schematic of the simulated deposition chamber is shown in Fig. 3a. Simulation results for the carrier velocity and diffusive ux are plotted in Fig. 3b for an inlet volumetric owrate of Q = 1000 SCCM, a chamber temperature of 600 K, substrate temperature of 300 K, background pressure P = 250 mTorr, chamber length and width of L = W = 1.8 m, respectively, inlet diameter of 0.2 m, exhaust ports of 0.2 m, and substrate size of 1.5 m. As outlined elsewhere,10 the simulated deposition rate is found to increase as Q and 1 / P under equilibrium source conditions. In Fig. 3c, the uniformity in the Gen-6 chamber is plotted as a function of the chamber length-to-width ratio L / W for W = 1.8 m at a background pressure of 250 mTorr and a variety of source ow rates. The deposition proles for one set of data at xed chamber dimensions L / W = 1.0 are shown in Fig. 3d. An optimal chamber ratio L / W = 0.75 is found to have 1.5%2.5% thickness nonuniformity for a range of deposition conditions while also minimizing the chamber volume. The material utilization efciency is found to be a weak function of L / W, and is primarily affected by the total ow rate, which dictates the degree of convective transport. The material usage efciency, therefore, decreases with increasing ow rate similar to the experimental data shown in Fig. 2, with M = 40% at Q = 500 SCCM and L / W = 1. While an increase in the diffusivity leads to an increase in M , changes in D0 have little effect. This suggests that the simulations semiquantitatively reect our experimental results despite uncertainties in the magnitude of the input modeling parameters. For this conguration, inlet velocities 0.25 m / s are necessary to avoid the formation of

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